DE2617589C2 - Use of special hydrophilic polyurethanes as agents against the reapplication of dirt and dirt dissolving agents for fiber fabrics - Google Patents

Description

H- (OC, H ₄ ) "- OH

in the ι

η such a number means that the molecular weight is between 300 and 10,000,

0 to 25% by weight of a diol (b) having a molecular weight below 300 and

1 to 20% by weight of a nitrogen-containing compound (C)

with mobile hydrogen atoms of the general formula:

X ₁
R'- N

\

X:

in which R 'is an alkyl radical with fewer than 5 carbon atoms and X | and X ₂ , which are identical or different, denote hydroxyalkyl radicals, the total ratio of NCO to mobile hydrogen being between 0.7 and 1, the tertiary nitrogen being quaternized before or after the reaction with the diisocyanate (A), as means in Mixtures of detergents to prevent dirt from being drawn back up and dirt dissolving agent for fiber fabrics.

The invention relates to the use of special hydrophilic polyurethanes as an anti-recovery agent

dragging and re-soiling when washing or finishing textiles, especially polyester fiber h

containing textiles. j \

FR-PS 14 16 463 describes the production of stable aqueous latices from polyurethanes. \ ·>

These latices are used to make textiles water-repellent. As a reaction partner for polyiso- \

cyanate, very different polyhydroxy compounds are given, such as polyethers, polyesters, polyester amides, Polyacetates and polythioethers, with polyethers also polymerisation products of tetrahydrofuran, of propylene, of ethylene as well as copolymerization products and graft polymers such as addition products of alkylene oxides and polystyrene are mentioned.

DE-AS 11 27 082 describes the production of water-soluble or water-swellable polyether urethanes %

known. A mixture of essentially linear polyethylene glycol or adducts of ethylene oxide with low molecular weight polyhydric alcohols or polyglycols with a molecular weight of 7500 or higher and diols, dicarboxylic acids or diamines with molecular weights of 200 to 2000 are used as reactants of the polyisocyanates. 3-20% by weight of diols or the other compounds mentioned, based on linear polyethylene glycol, are used, with higher proportions resulting in decreasing water-solubility, ¹ ^

lead. Polyisocyanates are used in an equivalent amount to the mixture of the reactants. The '

water-soluble products can be used for different purposes, e.g. B. for films, fibers, as Thickener, as an emulsifier or as a separating agent for oil / water.

The object of the invention is to create a means that prevents the redeposition of dirt on textiles avoids during the washing process.

This object is achieved according to the patent claim. '

It has been found, completely surprising, that special hydrophilic polyurethanes in wash liquors cause redeposition Avoid dirt on fiber fabric and also develop a dirt-loosening effect.

This effect is based on a selection of a special combination of polyhydroxy compounds as Reactants of polyisocyanates.

The hydrophilic polyurethane to be used according to the invention originates from the reaction of: 10 to 45% by weight of an organic diisocyanate (A),

89 to 35% by weight of a mixture (B) of compounds which contain one or two mobile hydrogen atoms, the mixture being formed from:
W) 100 to 75% by weight of a compound (a) of the general formula

H- (O-CjIIj) ₁₁ -OII

in the
<ö η means a number such that the molecular weight is between 300 and 10,000,

0 to 25% by weight of a diol (b) and

1 to 20% by weight of a compound (C) containing sugar

with mobile hydrogen atoms of the general formula

R '-N

X ₃ *

in which R 'is an alkyl radical with fewer than 5 carbon atoms and X | and X ₂ , which can be the same or different. Hydroxyalkyl or aminoalkyl radicals, the tertiary nitrogen being quaternized before or after the reaction with the diisocyanate A, the total ratio of NCO to mobile hydrogen (NCO / H) being between 0.7 and 1.

All aromatic, aliphatic or cycloaliphatic organic diisocyanates can be used according to the invention can be used. However, few of them are used more often because of their cheap availability. These are essentially tolylene diisocyanates, di (isocyanatophenyl) alkanes such as di (isocyanatophenyl) methane and di (isocyanatocyclohexyl) alkanes such as diOsocyanatocyclohexyl / methane. you will be used in amounts of 10 to 45 wt .-% of the polyurethane product.

The compound a) is preferably a polyoxyalkylene glycol with a molecular weight between 300 and 4000.

Compound b) is a diol, preferably a molecular weight below 300. From this class one can in particular the saturated diols such as the alkanediols or alkylene glycols, e.g. B. Ethylene glycol, the propylene glycols such as butylene glycol, diethylene glycol, triethylene glycol or tetraethylene glycol.

The proportions of compounds a) and b) in mixture B are between 100 and 75% by weight or 0 and 25% by weight, i.e. This means that in certain cases compound b) is not used.

Compound C corresponds to the general formula

25 X,

R '-N

Λ2

in which R 'is an alkyl group with fewer than 5 carbon atoms and X, and X ₂ , which are identical or different. Hydroxyalkyl or aminoalkyl radicals preferably having fewer than 5 carbon atoms. In this class, preference is given in particular to the N-alkyl diethanolamines or the N-alkyldipropanolamines, the N-alkyliminobispropylamines, N-alkylaminopropylethanolamines or N-alkylaminopropylpropanolamines, the alkyl radical containing fewer than 5 carbon atoms. A variant of the invention consists in that the tertiary nitrogen of the compound C is quaternized. This quaternization can take place either before the reaction of the mixture B with the diisocyanate or after the formation of the polyurethane. In both cases it is carried out with the help of classic quaternizing agents such as methyl sulfate or methyl or benzyl chlorides.

The nitrogen-containing compound C constitutes 1 to 20 weight percent of the polyurethane product. Another kind To define the proportion of this compound is to consider the proportion of tertiary nitrogen in the polyurethane product determined in% by weight. According to the invention, this percentage is between 0.1 and 2% by weight.

According to the invention, the total ratio of NCO groups introduced by the diisocyanate to mobile hydrogen introduced by compounds a) and b) of mixture B and by compound C is between 0.7 and 1, ie the reaction always takes place in the presence of excess mobile hydrogen atoms.
tv The reaction conditions under which the diisocyanate A with the compounds with mobile water

react with substances are common for the formation of a polyurethane. The reaction can optionally be carried out in Presence of a non-hydroxylated solvent, preferably a water-miscible solvent such as acetone, methyl ethyl ketone or dimethylformamide, can be carried out.

It is convenient to write the diisocyanate in the mixture of compounds with mobile hydrogen atoms, and to regulate this addition so that the temperature is kept between 20 and 15O ⁰ C.

The following examples describe some products to be used according to the invention. All percentages and parts are given in parts by weight.

example 1
100 parts of the following mixture are allowed to react in a reactor with 50 parts of acetone:

A) Toluylene diisocyanate (commercial mixture of 2,4- and 2,6-isomers 80:20) 33%

B) Mixture of: 62.8%

a) 88.5 parts by weight of polyoxyethylene glycol, MW 1500

b) 11.5 parts by weight of ethylene glycol

C) N-methyldiethanolamine 4.2% 1.5

The diisocyanate is introduced into the mixture of B and C for about 1 hour, the temperature between 30 and 40 ° C is maintained and the reaction until the disappearance of free NCO groups for a further 2 h

is allowed to run. 4.4 parts by weight of dimethyl sulfate are then added in order to quaternize the tertiary nitrogen of compound C. After 2 hours of reaction, 250 parts of water are added to the reaction mixture and the acetone is distilled off by evaporation in vacuo. A clear aqueous solution of product 1 according to the invention is obtained in this way. The 1% strength solution of the product becomes cloudy at 69 ^° C.

Example 2 The following mixture is reacted under the same conditions as in Example 1:

A) toluylene diisocyanate 32.5%

B) Mixture of: 59.3%

a) 92 parts by weight of polyoxyethylene glycol, MW 1500

b) 8 parts by weight of ethylene glycol

C) N-methyl diethanolamine 8.2%

The tertiary nitrogen of the product obtained is quaternized with 8.7 parts of methyl sulfate. The cloud temperature of a 1% strength solution of the product 2 thus obtained is 67.degree.

Example 3

The following mixture is reacted under the same conditions as in Example 1:

A) toluylene diisocyanate 35.8%

B) polyoxyethylene glycol, MW 300 59.7% C) N-methyl diethanolamine 4.5%

The tertiary nitrogen of the product thus obtained is quaternized with 4.8 parts of dimethyl sulfate. The cloud temperature a 1% solution of the product 3 is 20.degree.

Example 4

The following mixture is reacted under the same conditions as in Example 1:

A) toluene diisocyanate 33.7%

B) Mixture of: 62%

90.7 parts by weight of polyoxyethylene glycol, MW 600
9.3 parts by weight of ethylene glycol

C) N-methyldiethanolamine 4.3%

The tertiary nitrogen of the product thus obtained is quaternized with 4.45 parts of dimethyl sulfate. The cloud temperature a 1% solution of the product 4 is 52 to 53 ° C.

Example 5
The following mixture is reacted under the same conditions as in Example 1:

A) Di (4-isocyanatophenyl) methane 18.9%

B) polyoxyethylene glycol, MW 1500 75.7%

C) N-methyl diethanolamine 5.4%

The tertiary nitrogen of the product obtained is quaternized with 5.4 parts of dimethyl sulfate. The cloud temperature of a 1% solution of the product 5 thus obtained is above 100 ^° C.

Example 6

The following mixture is reacted under the same conditions as in Example 1:

A) toluylene diisocyanate 30.9%

B) Mixture of: 65.3% 6 (i 80.5 parts by weight of polyoxyethylene glycol, MW 4000

19.5 parts by weight of ethylene glycol

C) N-methyldiithanol gum 3.8%

The tertiary nitrogen of the product obtained is quaternized with 4.0 parts of dimethyl sulfate. The cloud point temperature of a l% solution of the product igcn 8 thus obtained is 6O ⁰ C.

Example 7
LI liter the same conditions as in Example 1, the following mixture is implemented:

Λ) Toluylene diisocyanate 33% ^

B) Mixture of: 62.8%

a) 55.6 parts by weight of polyoxyethylene glycol, MW 1500

32 parts by weight of a nonylphenol which carries 30 moles of ethylene oxide,

b) 12.4 parts by weight of ethylene glycol

C) N-methyldiethanolamine 4.2% io

The tertiary nitrogen of the product thus obtained is quaternized with 4.45 parts of dimethyl sulfate. The cloud temperature a 1% solution of the product 9 thus obtained is 62 ° C.

Example 8 15

The components of the mixture described in Example 1 are reacted in the following order: in a reactor, the polyoxyethylene glycol, the ethylene glycol and N-methyldiethanolamine are Man and heated to 70 ⁰ C. Then, to the dimethyl sulphate, which can react for 1 hour leaves. Subsequently, the toluene diisocyanate is added over 2 hours while maintaining the temperature of 130-135 ⁰ C. The water is then added at 130 to 135 ° C. with stirring. DieTrübungstemperalurdes product 10 thus obtained is 67 ⁰ C.

Example 9
The following mixture is reacted under the same conditions as in Example 1:

A) toluene diisocyanate 20.6%

B) Mixture of: 79.4%

94.7 parts by weight of polyoxyethylene glycol, MW 1500.? O

5.3 parts by weight of ethylene glycol

C) N-methyl diethanolamine 0.0%

The product 11 obtained does not fall within the scope of the invention because it does not contain any compound C. The cloud temperature of a 1% solution is 31 ° C. .15

Example 10
The following mixture is reacted under the same conditions as in Example 1:

A) toluene diisocyanate 33.03%

B) Mixture of: 62.78% 88.64 parts by weight of polyoxyethylene glycol, MW 1500

11.38 parts by weight of ethylene glycol

C) N-methyl diethanolamine 4.18% 45

The tertiary nitrogen of the product obtained is quaternized with 4.45 parts of benzyl chloride.

Example 11
The representation is identical to that described in Example 12, but the tertiary nitrogen is quaternized with 8.75 parts of lauryl bromide.

Example 12

55 The following mixture is reacted under the same conditions as in Example 1:

A) toluylene diisocyanate 33.00%

B) mixture of polyoxyethylene glycol 62.82%

37.20 parts by weight of polyoxyethylene glycol, MW 1500 60

51.15 parts by weight ethoxy obtained by condensation with 30 mol of ethylene oxide

lated nonylphenol
11.64 parts by weight of ethylene glycol

C) N-methyl diethanolamine 4.18%

The tertiary nitrogen of the product obtained is quaternized with 4.42 parts of dimethyl sulfate.

Example 13

The representation according to Example 1 is repeated, except that the amount of ethylene added is ftj

glycols in such a way that the following hydroxyl numbers are obtained for the end product: r ' ¹

a) ll, 2mgK0H / g §.

b) 17.5 mgKOH / g ||

c) 27.6 mg KOH / g I ^s ;

d) 38.3 mg KOH / g | i

The compounds described above were found to be excellent anti-redeposition agents and against re-soiling when they are drawn onto textile fibers in any known manner are. An agent against re-pollution is understood to mean a product that removes Stains from tissues on which it is drawn relieved.

Indeed, it is known that fabrics with a significant proportion of polyester fibers have a tendency to to be very hydrophobic. Due to these properties, grease stains on the fabric are deposited fixed, which makes their removal difficult. Another well-known disadvantage of polyester fibers is that the dirt in the washing bath can be drawn back onto the fabric during washing. One of the means to prevent dirt from being redrawn and to facilitate the removal of grease stains consists in applying a finish to the fibers which gives them a certain hydrophilic property gives.

It has been found that the products described above represent a finishing agent which imparts the desired hydrophilic property to the polyester fibers to which they are drawn.
The water-soluble products can be absorbed in any known manner, ie in particular therein

:> insist that a finish is applied by padding or spraying after dyeing on the raw fabric or on the textile article after washing by the user. However, the products are preferably applied during the washing of the fabrics, ie the water-soluble polyurethanes are introduced either into the detergents or into the rinse bath.
The addition of the products according to the invention can be in any type of detergent mixture, anionic,

.ίο non-ionic, cationic, ampholytic or zwitterionic. These mixtures contain in generally, in addition to surfactants and builders, a certain number of classic ingredients in changing amounts. Examples of these components are foam stabilizers or, on the contrary, agents to reduce foam development such as polysiloxanes, inorganic salts such as sodium sulfate, bleach, those alone or in admixture with pre-bleaches and other anti-redeposition agents, such as Carboxymethyl cellulose, as well as small amounts of perfumes, dyes, brighteners and Enzymes.

The incorporation of these ingredients can be carried out in any known manner, e.g. B. by addition in the form of a solution or emulsion during the spray-drying of the powder mixtures or in granular form into the aforesaid Mixtures are made. The addition to liquid household or industrial detergents can also be added known techniques are easily done.

The use according to the invention is illustrated in the following example.

Example 14

Squares (12X12 cm) of polyester-cotton fabric (67/33) are washed in a Lini-Test machine (original HANAU) for 20 min at 6O ⁰ C in hard water (33 ° TH) containing 0.75 g / I of the following classic detergent mixture contains:

chain alkylbenzenesulfonate (alkyl with about 12 carbon atoms) 8%

so alcohol with 16 to 18 carbon atoms and about 50 ethylene oxide units 3%

natural fat soap 4%

Sodium tripolyphosphate 30%

Sodium orthophosphate 1.5%

Sodium pyrophosphate 12.5%

Sodium perborate 25%

Sodium sulfate 10%

Sodium disilicate 6%

A test soil according to Spangler (see J. Am. Oil Chem. Soc. 1965, 42, 723-727) is placed in each washing vessel. in an amount of 5% by weight of the wash liquor. The product according to the invention is used in an amount of 3% by weight, based on the detergent mixture to which it is added, added.

The reapplication of the Spanglcr test soil on the fabric is assessed on the basis of the difference in the reflection Λ R compared to a comparison fabric which is washed without the product according to the invention. The reflection is measured with a Gardner apparatus (Gardner Instruments).

Some of the products described above were used as shown in the table below Get values:

Tested product

12 3 4 7

Δ R +12 +8 +6 +11 +8

Under these test conditions, the measurement accuracy is 1. In the following example, the The dirt-dissolving property of the water-soluble products in an anionic washing liquor made clear.

Example 15

For strips (20 x 115 cm) of polyester / cotton / fabric (6733) of reflection C , washing is carried out in an automatic Miele 421 S (color program -6O ⁰ C) in the presence of 5 g / l of the following classic detergent mixture:

chain alkylbenzenesulfonate (alkyl of about 12 carbon atoms) 9.9%: o

Alcohol with 16 to 18 carbon atoms and about 15 oxyethylene units 5%

natural fat soap 6.6%

Sodium tripolyphosphate 34%

Sodium orthophosphate 0.9%

Sodium pyrophosphate 2.3%

Sodium perborate 22.9%

Sodium sulfate 4.8%

Sodium disilicate 5.4%

Carboxymethyl cellulose 0.6%

Water 7.6%: -n

The product investigated is added in an amount of 3% by weight, based on the detergent in which it is incorporated. The fabric strips are then dried at room temperature and cut into squares (12 x 12 cm), to which used oil, Spangler test dirt, tomato concentrate and lipstick are applied for 6 squares per type of dirt. The spots are then aged by einslündigen stay in a heat chamber at 60 ⁰ C. The reflection R is measured on an Elrepho apparatus with an FM Y / C filter for used oil and Spangler test dirt and an FM X / C filter for tomato concentrate and lipstick.

The soiled squares are then attached to 10 clean cotton rags, then as before washed and dried. Then you measure their reflection /?,. The effective wedge of the tested product as Soil release agent is rated by the percentage of stain removal, which is determined by the following formula is calculated

For each product tested, calculate the mean percentage of removal of the different ones Stains. The results are given in the following table:

Tested product

^{equal to} 1 2 3 4 5 7 11 12 13 14 15a 15b 15c 15d

£ in% 40 58 55 46 48 47 50 40 50 47 50 58 56 52 46

Under these test conditions, the measurement accuracy is 1. In the following example, the The dirt-dissolving property of the water-soluble products in a non-ionic washing liquor made clear.

Example 16 <, o

The experiments are carried out under the same conditions as in Example 15, but with the following nonionic Washing liquor, carried out:

Alcohol with 10 to 12 carbon atoms and an average of 5 oxyethylene units 9.4%

Sodium tripoly-phosphate 31.4%

Sodium orthophosphate 1 i%

Nutrium pyrophosphate 7.3%

Nutriimperboral 26.2%

Sodium sulfate 15.8%

Sodium disilicate 8.5%

Polysiloxane (foam reducing agent) 0.3%

The results are given in the table below.

Comparison of tested product

1 2 4 7 11

E in% 56 68 62 65 73 56

The following example shows the dirt-dissolving properties of the water-soluble products, added during the final rinse of a bleaching process.

Example 17

Two strips (20 x 115 cm) of polyester / cotton / fabric (67/33) of reflection C are in one Miele 421 S machine (color program) washed in the presence of 5 g / l of the following detergent:

chain alkylbenzenesulfonate 9.9%

Alcohol with 16 to 18 carbon atoms and about 15 ethylene oxide units 5%

natural fat soap 6.6%

Sodium tripolyphosphate 34%

Sodium orthophosphate 0.9%

Sodium pyrophosphate 2.3%

Sodium perborate 22.9%

Sodium sulfate 4.8%

Sodium disilicate 5.4%

Carboxymethyl cellulose 0.6%

Water 7.6%

3 g of the tested product are added to a bleaching treatment in the course of the last wash. The fabric strips are then dried at room temperature and cut into squares (12 × 12 cm) on which used oil, Spangler test dirt, tomato concentrate and lipstick are applied in 6 squares for each type of stain. The stains are then aged by staying in a heating cabinet at 60 ^{° C. for one hour.} Its reflection R is then measured in an Elrepho apparatus with an FMY / C filter for used oil and Spangler test dirt and an FMX / C filter for tomato concentrate and red lipstick.

The stained squares are then attached to 10 clean cotton rags and with the Washed detergent described above at a concentration of 5 g / l. After drying, measurements are taken the reflection Λ, the ouadrate. The effectiveness of the tested product as a dirt-releasing agent is determined by the percentage of stain removal calculated according to the following formula:

£ (in%) = x 100.
C ~ R

The mean percentage removal of the various stains is then calculated. the Results of these tests are given in the following table:

Comparison of tested product

E in% 40 61

The measurement accuracy in this test is 1%. The following example uses the dirt-releasing Properties of the products according to the invention are illustrated when they are applied to the fabric by padding will.

Example 18

Two strips (20 x 115 cm) of polyester / cotton / fabric (67/33) of reflection C are immersed in a 2% aqueous solution of the tested product. After soaking for 15 minutes, the two strips are padded (degree of pressure 100%) and left to dry at room temperature.

The strips impregnated in this way are cut into squares (12 × 12 cm). On these squares one carries "

Used oil, Spangler test dirt, tomato concentrate and red lipstick with 6 squares for each type of stain. The stains are then aged by staying in a heating cabinet at 60 ^{° C. for one hour.} Its reflection R is then measured in an Elrepho device with an FMY / C filter door used oil and %

Spangler test dirt and an FMX / C filter for tomato concentrate and red lipstick. 5

The mischievous squares are then attached to 10 clean cotton rags and put in a Mieie 421 S machine (color program) in the presence of the following classic detergent a concentration of 5 g / l washed:

chain-like alkylbenzenesulfonate (alkyl with 12 carbon atoms) 9.9% ίο

Alcohol with 16 to 18 carbon atoms and about 15 ethylene oxide units 5%

natural fat soap 6.6%

Sodium tripolyphosphate 34%

Sodium orthophosphate 0.9% sodium pyrophosphate 2.3% 15

Sodium Perborate 22.9% Sodium Sulphate 4.8%

Sodium disilicate 5.4%

Carboxymethyl cellulose 0.6% water 7.6% 20

After washing and drying at room temperature, the reflection Λ, the tissue squares, is measured. the Soil dissolving effect of the tested product is due to the percentage of stain removal rated. This percentage is calculated using the following formula:

RR "

f (in%) = 45- ~ x 100.
CR

For each product tested, calculate the mean percentage for the removal of the different ones Stains. The results of these tests are given in the following table: 30

Comparison of tested product

7 1!

35

£ (in%) 37 60 45

40

45

Claims (1)

Claim: Use of hydrophilic polyurethanes obtainable by reactions of: 10 to 45% by weight of an organic diisocyanate (A),
89 to 35% by weight of a mixture (B) of compounds having one or two mobile hydrogen atoms, which is formed by: 100 to 75% by weight of a compound (a) of the general formula